Herbicidal composition

ABSTRACT

A selectively herbicidal composition for controlling grasses and weeds in crops of useful plats, comprising a) a herbicidally effective mixture of MCPA, bromoxynil and a compound of formula (I) wherein the substituents are as defined in claim  1  and b) an amount, effective for herbicide antagonism, of a compound of formula (II) wherein the substituents are as defined in claim  1 .

The present invention relates to new selectively herbicidal compositionsfor controlling grasses and weeds in crops of useful plants, especiallyin crops of cereals, maize and sorghum, which compositions comprise aherbicide and a safener (counter-agent, antidote) and protect the usefulplants but not the weeds against the phytotoxic action of the herbicide,and to the use of such a composition in controlling weeds in crops ofuseful plants.

The use of herbicides can result in considerable damage also beingcaused to cultivated plants, for example in dependence upon theconcentration of the herbicide and the mode of its application, thecultivated plant, the nature of the soil and the climatic conditions,such as period of exposure to light, temperature and amounts ofprecipitation. In order to counter those and similar problems, varioussubstances have already been proposed as safeners that are capable ofantagonising the damaging action of the herbicide on the cultivatedplant, that is to say of protecting the cultivated plant against thataction, while the herbicidal action on the weeds to be controlled isvirtually unimpaired. It has been found that the proposed safeners oftenhave a very specific action both in respect of the cultivated plants andin respect of the herbicide and in some cases also in dependence uponthe mode of application. This means that a specific safener is oftensuitable only for a specific cultivated plant and a particular class ofherbicide or a specific herbicide. For example, compounds known from EP94 349, WO 96/21652 and WO 99/47525 protect the cultivated plantsagainst the phytotoxic action of herbicides such as, for example, the3-hydroxy-4-aryl-5-oxo-pyrazoline derivatives known from WO 96/21652 andWO 99/47525.

It has now been found that the compounds of formula II

wherein

-   -   Rs₁ is hydrogen or chlorine and Rs₂ is hydrogen, C₁-C₈alkyl, or        Cl-C₈alkyl substituted by C₁-C₆alkoxy or by C₃-C₆alkenyloxy,    -   are suitable for protecting cultivated plants against the        phytotoxic action of a mixture of        3-hydroxy-4-aryl-5-oxo-pyrazoline herbicides known from WO        01/17353, MCPA and bromoxynil. MCPA and bromoxynil are described        in The Pesticide Manual, Twelfth Edition, 2000, Entry Nos. 93,        and 485 and 486.

There is accordingly proposed, in accordance with the invention, aselectively herbicidal composition that, in addition to comprisingcustomary inert formulation adjuvants such as carriers, solvents andwetting agents, comprises as active ingredient a mixture of

-   -   a) a herbicidally effective amount of a mixture of MCPA,        bromoxynil and a herbicide of formula I        wherein R₁ and R₃ are each independently of the other ethyl,        haloethyl, ethynyl, C₁- or C₂-alkoxy, C₁- or C₂-haloalkoxy, C₁-        or C₂-alkylcarbonyl or C₁- or C₂-hydroxyalkyl;    -   R₄ and R₅ together are a group        Z₂-CR₁₄(R₁₅)—CR₁₆(R₁₇)—O—CR₁₈(R₁₉)-CR₂₀(R₂₁)-(Z₂);    -   R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀ and R₂₁, are each        independently of the others hydrogen, halogen, C₁-C₄alkyl or        C₁-C₄haloalkyl, it being possible for an alkylene ring to be        either fused or spiro-linked to the carbon atoms of the group        Z₂, which alkylene ring contains, together with the carbon atoms        of the group Z₂ to which it is bonded, from 2 to 6 carbon atoms        and may be interrupted by oxygen, or that alkylene ring bridges        at least one ring atom of the group Z₂;    -   G is hydrogen, —C(X₁)—R₃₀, —C(X₂)—X₃—R₃₁, —C(X₄)—NR₃₂(R₃₃),        —S(O)₂—R₃₄, —P(X₅)R₃₅R₃₆, —CH₂—X₆—R₃₇ or an alkali metal cation,        alkaline earth metal cation, sulfonium cation or ammonium        cation;    -   X₁, X₂, X₃, X₄, X₅ and X₆ are each independently of the others        oxygen or sulfur;    -   R₃₀, R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆ and R₃₇ are each independently        of the others hydrogen,    -   C₁-C₁₀alkyl, C₁-C₁₀haloalkyl, C₁-C₁₀cyanoalkyl,        C₁-C₁₀nitroalkyl, C₁-C₁₀aminoalkyl, C₂-C₅-alkenyl,        C₂-C₅haloalkenyl, C₃-C₈cycloalkyl, C₁-C₅alkylamino-C₁-C₅alkyl,        di(C₁-C₅alkyl)amino-C₁-C₅alkyl, C₃-C₇cycloalkyl-C₁-C₅alkyl,        C₁-C₅alkoxy-C₁-C₅alkyl, C₃-C₅alkenyloxy-C₁-C₅alkyl,        C₃-C₅alkynyloxy-C₁-C₅alkyl, C₁-C₅alkylthio-C₁-C₅alkyl,        C₁-C₅alkylsulfoxyl-C₁-C₅alkyl, C₁-C₅-alkylsulfonyl-C₁-C₅alkyl,        C₂-C₈alkylideneaminooxy-C₁-C₅alkyl,        C₁-C₅alkylcarbonyl-C₁-C₅alkyl, C₁-C₅alkoxycarbonyl-C₁-C₅alkyl,        C₁-C₅alkylaminocarbonyl-C₁-C₅alkyl,        di(C₁-C₅alkyl)amino-carbonyl-C₁-C₅alkyl,        C₁-C₅alkylcarbonylamino-C₁-C₅alkyl,        C₁-C₅alkylcarbonyl(C₁-C₅alkyl)-amino-C₁-C₅alkyl, tri(C₁- or        C₂-alkyl)silyl-C₁-C₅alkyl, phenyl, heteroaryl,        phenyl-C₁-C₅alkyl, heteroaryl-C₁-C₅alkyl, phenoxy-C₁-C₅alkyl or        heteroaryloxy-C₁-C₅alkyl, it being possible for the        afore-mentioned aromatic rings to be substituted by halogen,        nitro, cyano, amino, di(C₁-C₄alkyl)amino, hydroxy, methoxy,        ethoxy, methylthio, ethylthio, formyl, acetyl, propionyl,        carboxyl, C₁-C₅alkoxycarbonyl or by C₁- or C₂-haloalkyl; R₃₄,        R₃₅ and R₃₆ are, in addition, C₁-C₁₀alkoxy, C₁-C₁₀haloalkoxy,        C₁-C₅alkylamino, di(C₁-C₅-alkyl)amino, benzyloxy or phenoxy, it        being possible for the aromatic rings of the last two        substituents to be substituted by halogen, nitro, cyano, amino,        dimethylamino, hydroxy, methoxy, ethoxy, methylthio, ethylthio,        formyl, acetyl, propionyl, carboxyl, C₁-C₅alkoxy-carbonyl or by        C₁- or C₂-haloalkyl; and    -   R₃₇ is, in addition, C₁-C₁₀alkylcarbonyl,    -   or a salt or diastereoisomer of a compound of formula I, and    -   b) an amount, effective for herbicide antagonism, of a safener        of formula II        wherein Rs₁ is hydrogen or chlorine and Rs₂ is hydrogen,        C₁-C₈alkyl, or C₁-C₈alkyl substituted by C₁-C₆alkoxy or by        C₃-C₆alkenyloxy.

Preferred selectively herbicidal compositions comprise, as compound offormula II, a compound of that formula wherein Rs₁ is chlorine and Rs₂is C₁-C₈alkyl.

Herbicides of formula I to which preference is given for the compositionaccording to the invention are those wherein R₁ and R₃ are eachindependently of the other ethyl, haloethyl, ethynyl, C₁- or C₂-alkoxyor C₁- or C₂-haloalkoxy.

Further preferred compositions comprise, as compound of formula I, acompound of that formula wherein R₄ and R₅ together form a groupZ₂-CR₁₄(R₁₅)—CR₁₆(R₁₇)—O—CR₁₈(R₁₉)—CR₂₀(R₂,)—

-   -   wherein R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀ and R₂₁ are hydrogen.

Preference is furthermore given to those compositions that comprise, ascompound of formula I, a compound of that formula wherein G is hydrogen,—C(X₁)—R₃₀, —C(X₂)—X₃—R₃₁, —C(X₄)—NR₃₂(R₃₃), —S(O)₂—R₃₄, —P(X₅)R₃₅R₃₆,—CH₂—X₅—R₃₇ or an alkali metal cation, alkaline earth metal cation,sulfonium cation or ammonium cation; X₁, X₂, X₃, X₄, X₅ and X₆ are eachindependently of the others oxygen or sulfur; R₃₀, R₃₁, R₃₂, R₃₃, R₃₄,R₃₅, R₃₆ and R₃₇ are each independently of the others hydrogen,C₁-C₈alkyl, C₁-C₈haloalkyl, C₁-C₈cyanoalkyl, C₁-C₈-nitroalkyl,C₁-C₈aminoalkyl, C₂-C₅alkenyl, C₂-C₅haloalkenyl, C₃-C₈cycloalkyl,C₁-C₅alkylamino-C₁-C₂alkyl, di(C₁-C₅alkyl)amino-C₁-C₂alkyl,C₃-C₇cycloalkyl-C₁-C₂alkyl, C₁-C₄alkoxy-C₁-C₄-alkyl,C₂-C₄alkenyloxy-C₁-C₄alkyl, C₃-C₄alkynyloxy-C₁-C₄alkyl,C₁-C₄alkylthio-C₁-C₄alkyl, C₁-C₂alkylsulfoxyl-C₁-C₂alkyl,C₁-C₂alkylsulfonyl-C₁-C₂alkyl, C₂-C₈alkylideneaminooxy-C₁-C₂-alkyl,C₁-C₅alkylcarbonyl-C₁-C₂alkyl, C₁-C₆alkoxycarbonyl-C₁-C₂alkyl,C₁-C₅alkylamino-carbonyl-C₁-C₂alkyl,di(C₁-C₄alkyl)aminocarbonyl-C₁-C₂alkyl,C₁-C₅alkylcarbonylamino-C₁-C₂-alkyl,C₁-C₂alkylcarbonyl(C₁-C₃alkyl)amino-C₁-C₂alkyl, tri(C₁- orC₂-alkyl)silyl-C₁-C₃alkyl, phenyl, heteroaryl, phenyl-C₁-C₂alkyl,heteroaryl-C₁-C₂alkyl, phenoxy-C₁-C₂alkyl or heteroaryloxy-C₁-C₂alkyl;R₃₄, R₃₅ and R₃₆ are, in addition, C₁-C₆alkoxy, C₁-C₆haloalkoxy,C₁-C₃alkylamino, di(C₁-C₃alkyl)amino, benzyloxy or phenoxy, it beingpossible for the aromatic rings of the last two substituents to besubstituted by halogen, nitro, cyano, amino, dimethylamino, hydroxy,methoxy, ethoxy, methylthio, ethylthio, formyl, acetyl, propionyl,carboxyl, C₁-C₅alkoxycarbonyl or by C₁- or C₂-haloalkyl; and

-   -   R₃₇ is, in addition, C₁-C₈alkylcarbonyl.

Of those compositions, special preference is given to those comprising,as compound of formula I, a compound of that formula wherein G ishydrogen, —C(X₁)—R₃₀, —C(X₂)—X₃—R₃₁, —C(X₄)—NR₃₂(R₃₃), —S(O)₂—R₃₄,—P(X₅)R₃₅R₃₆, —CH₂—X₆—R₃₇ or an alkali metal cation, alkaline earthmetal cation, sulfonium cation or ammonium cation; X₁, X₂, X₃, X₄, X₅and X₆ are each independently of the others oxygen or sulfur; R₃₀, R₃₁,R₃₂, R₃₃, R₃₄, R₃₅, R₃₆ and R₃₇ are each independently of the othershydrogen, C₁-C₈alkyl, C₁-C₈haloalkyl, C₂-C₅alkenyl, C₂-C₅halo-alkenyl,C₃-C₈cycloalkyl, C₃-C₇cycloalkyl-C₁-C₂alkyl, C₁-C₄alkoxy-C₁-C₄alkyl,phenyl, heteroaryl, phenyl-C₁-C₂alkyl, heteroaryl-C₁-C₂alkyl,phenoxy-C₁-C₂alkyl or heteroaryloxy-C₁-C₂-alkyl; R₃₄, R₃₅ and R₃₆ are,in addition, C₁-C₆alkoxy, C₁-C₃alkylamino, di(C₁-C₃alkyl)amino;

-   -   and R₃₇ is, in addition, C₁-C₈alkylcarbonyl.

Of very special value are those compositions that comprise a) a mixtureof MCPA, bromoxynil and a herbicide of formula I wherein G is hydrogenor —C(X₂)—X₃—R₃₁, wherein X₂ and X₃ are oxygen, and R₃₁ is tert-butyl,and b) a safener of formula II wherein Rs₁ is chlorine and Rs₂ is1-methylcyclohexyl.

The invention relates also to a method for the selective control ofweeds in crops of useful plants, which method comprises treating theuseful plants, their seeds or cuttings or the crop area thereof,simultaneously or separately, with a) a herbicidally effective amount ofa mixture of MCPA, bromoxynil and a compound of formula I, b) an amount,effective for herbicide antagonism, of a safener of formula II and,optionally, c) an additive comprising an oil of vegetable origin, or analkylated derivative thereof, or a mineral oil, or a mixture thereof.

Cultivated plants that may be protected against the harmful effect ofthe above-mentioned herbicides by means of the safeners of formula IIare especially cereals, maize and sorghum. Crops are to be understood asincluding those that have been made tolerant to herbicides or classes ofherbicides by means of conventional breeding or genetic engineeringmethods, for example IMI Maize, Poast Protected Maize (sethoxydimtolerance), Liberty Link Maize, B.t./Liberty Link Maize, IMI/LibertyLink Maize, IMI/Liberty Link /B.t. Maize, Roundup Ready Maize andRoundup Ready/B.t. Maize.

The weeds to be controlled may be either monocotyledonous ordicotyledonous weeds such as, for example, Stellaria, Nasturtium,Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum,Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus,Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium,Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola andVeronica.

Crop areas are areas of land on which the cultivated plants are alreadygrowing or in which the seeds of those cultivated plants have been sown,and also land on which it is intended to grow those cultivated plants.

A safener of formula II may, depending on the intended purpose, be usedto pre-treat the seed material of the cultivated plant (dressing theseed or the cuttings) or may be incorporated into the soil before orafter sowing. It may, however, also be applied, alone or together withthe herbicide and, optionally, the oil additive, after the emergence ofthe plants. The treatment of the plants or seed with the safener cantherefore, in principle, be effected independently of the time at whichthe herbicide is applied. The treatment of the plants can, however, alsobe carried out by applying the herbicide and safener simultaneously (forexample in the form of a tank mixture). The rate of application of thesafener in relation to the herbicide depends largely on the method ofapplication. In the case of field treatment, which is effected eitherusing a tank mixture with a combination of the safener and the herbicideor by the separate application of the safener and the herbicide, theratio of herbicide (or herbicide mixture) to safener is generally from1:100 to 100:1, preferably from 1:10 to 10:1, and especially from 1:5 to5:1.

In the case of field treatment, from 0.001 to 5.0 kg of safener/ha,preferably from 0.001 to 0.5 kg of safener/ha, are generally applied.The rate of application of herbicide (or herbicide mixture) is generallyfrom 0.001 to 2 kg/ha, but preferably from 0.005 to 0.5 kg/ha.

The compositions according to the invention may, in addition, compriseadditives comprising an oil of vegetable origin, or an alkylatedderivative thereof, or a mineral oil, or a mixture thereof. Preferably,such additives are added to the spray tank (tank mixture);advantageously in an amount of from 0.01 to 2%, based on the spraymixture. The additive can, for example, be added to the spray tank inthe desired concentration after the spray mixture has been prepared.Preference is given to additives comprising oils of vegetable origin.Special preference is given to additives comprising, for example, thefollowing components (A) from 20 to 90% by weight of alkyl esters ofhigher (C₄-C₂₂) fatty acids, (B) from 4 to 40% by weight of anionic ornon-ionic surfactants, (C) from 2 to 20% by weight of higher (C₁₀-C₂₀)fatty acids, and (D) up to 140% by weight, based on the total amount ofcomponents (A) to (C), of hydrocarbons.

Especially suitable additives comprise, as component (A), alkyl estersof higher (C₈-C₂₂) fatty acids, especially the C₁-C₄alkyl esterderivatives of C₁₂-C₁₈ fatty acids, for example the methyl esters oflauric acid, palmitic acid and oleic acid. Those esters are known asmethyl laurate (CAS-111-82-0), methyl palmitate (CAS-112-39-0) andmethyl oleate (CAS-112-62-9). The application and action of theadditives can be improved by combining them with surface-activesubstances such as, for example, anionic surfactants (B). Examples ofsuitable anionic surfactants are surfactants of thedodecylbenzylsulfonate type, especially the calcium salts thereof. Theconcentration of the surface-active substances, based on the totaladditive, is generally from 1 to 30% by weight. Preferred higher fattyacids (C) contain from 12 to 18 carbon atoms.

The presence of an organic solvent (D) can, furthermore, bring about afurther increase in action. Preferred solvents (D) are, for example,aromatic solvents such as Solvesso® (ESSO) or Aromatic Solvent® (ExxonCorporation) types. The concentration of those solvents can be from 10to 80%, by weight, of the total weight. Such oil additives aredescribed, for example, in U.S. Pat. No.4,834,908. They are especiallypreferred for the composition according to the invention. An oiladditive to which very special preference is given is known under thename MERGE®. In the compositions according to the invention there mayaccordingly be used, as preferred additive, an additive comprising (A)C₁-C₄alkyl esters of C₁₂-C₁₈ fatty acids, (B) anionic surfactants of thedodecylbenzylsulfonate type, (C) C₁₂-C₁₈ fatty acids, and (D) aromatichydrocarbons.

The compositions according to the invention are suitable for all methodsof application that are customary in agriculture, for examplepre-emergence application, post-emergence application and seed dressing.In the case of seed dressing, from 0.001 to 10 g of safener/kg of seed,preferably from 0.05 to 2 g of safener/kg of seed, are generallyapplied. When the safener is applied in liquid form shortly beforesowing, with swelling of the seed, it is advantageous to use safenersolutions that comprise the active ingredient in a concentration of from1 to 10 000 ppm, preferably from 100 to 1000 ppm.

For application, the safeners of formula II or combinations of thosesafeners with MCPA, bromoxynil and the herbicides of formula I and,optionally, the additives are advantageously processed, together withthe adjuvants conventionally employed in formulation technology, intoformulations, for example into emulsifiable concentrates, coatablepastes, directly sprayable or dilutable solutions, dilute emulsions,wettable powders, soluble powders, dusts, granules or microcapsules.Such formulations are described, for example, in WO 97/34485, on pages 9to 13. The formulations are prepared in known manner, for example byintimately mixing and/or grinding the active ingredients with liquid orsolid formulation adjuvants, for example solvents or solid carriers.Furthermore, surface-active compounds (surfactants) may additionally beused in the preparation of the formulations. Solvents and solid carriersthat are suitable for that purpose are mentioned, for example, in WO97/34485 on page 6.

Suitable surface-active compounds are, depending on the nature of theactive ingredient being formulated, non-ionic, cationic and/or anionicsurfactants and mixtures of surfactants having good emulsifying,dispersing and wetting properties. Examples of suitable anionic,non-ionic and cationic surfactants are listed, for example, in WO97/34485 on pages 7 and 8.

Furthermore, the surfactants customarily employed in formulationtechnology, which are described, inter alia, in “Mc Cutcheon'sDetergents and Emulsifiers Annual” MC Publishing Corp., Ridgewood N.J.,1981, Stache, H., “Tensid-Taschenbuch”, Carl Hanser Verlag,Munich/Vienna, 1981 and M. and J. Ash, “Encyclopedia of Surfactants”,Vol I-III, Chemical Publishing Co., New York, 1980-81, are also suitablefor preparation of the herbicidal compositions according to theinvention.

The herbicidal formulations generally comprise from 0.1 to 99% byweight, especially from 0.1 to 95% by weight, of active ingredientmixture comprising MCPA, bromoxynil and the compound of formula Itogether with the compounds of formula II, from 0 to 2% by weight of theoil additive, from 1 to 99.9% by weight of a solid or liquid formulationadjuvant and from 0 to 25% by weight, especially from 0.1 to 25% byweight, of a surfactant. Whereas commercial products will preferably beformulated as concentrates, the end user will normally employ diluteformulations.

The compositions may also comprise further additives such asstabilisers, for example vegetable oils or epoxidised vegetable oils(epoxidised coconut oil, rapeseed oil or soybean oil), antifoams, forexample silicone oil, preservatives, viscosity regulators, binders andtackifiers, as well as fertilisers or other active ingredients. Thereare various suitable methods and techniques for using safeners offormula II or compositions comprising them for protecting cultivatedplants against harmful effects of the mixture of MCPA, bromoxynil andthe herbicide of formula I; the following are examples:

i) Seed Dressing

a) Dressing the seeds with a wettable powder formulation of a compoundof formula II by shaking in a vessel until the formulation is uniformlydistributed over the seed surface (dry dressing). Approximately from 1to 500 g of compound of formula II (from 4 g to 2 kg of wettable powder)are used per 100 kg of seed.

b) Dressing the seeds with an emulsifiable concentrate of the compoundof formula II according to method a) (wet dressing).

c) Dressing by immersing the seed in a liquid formulation comprisingfrom 100 to 1000 ppm of compound of formula II for from 1 to 72 hoursand, if desired, subsequently drying the seeds (immersion dressing).

Dressing the seed or treating the germinated seedlings are naturally thepreferred methods of application because the treatment with the activeingredient is directed wholly at the target crop. Generally from 1 to1000 g of antidote, preferably from 5 to 250 g of antidote, are used per100 kg of seed, although, depending on the method employed, which alsoallows the addition of other active ingredients or micronutrients,amounts above or below the specified concentration limits may beemployed (repeat dressing).

ii) Application in the Form of a Tank Mixture

A liquid formulation of a mixture of antidote and herbicide (ratio ofthe one to the other from 10:1 to 1:100) is used, the rate ofapplication of herbicide being from 0.005 to 5.0 kg per hectare. Suchtank mixtures are applied before or after sowing.

iii) Application to the Seed Furrow

The compound of formula II is introduced into the open, sown seed furrowin the form of an emulsifiable concentrate, a wettable powder orgranules. After the seed furrow has been covered, the herbicide isapplied pre-emergence in the normal manner.

iv) Controlled Release of the Active Ingredient

The compound of formula II is applied in solution to granulated mineralcarriers or polymerised granules (urea-formaldehyde) and dried. Ifdesired, a coating may be applied (coated granules) which enables theactive ingredient to be released in metered amounts over a predeterminedperiod of time.

Preferred formulations have especially the following compositions(%=percent by weight; ‘active ingredient mixture’ denotes the mixture ofMCPA, bromoxynil and compound of formula I with the compound of formulaII)

Emulsifiable Concentrates:

active ingredient mixture: from 1 to 90%, preferably from 5 to 20%

surface-active agent: from 1 to 30%, preferably from 10 to 20%

liquid carrier: from 5 to 94%, preferably from 70 to 85%

Dusts:

active ingredient mixture: from 0.1 to 10%, preferably from 0.1 to 5%

solid carrier from 99.9 to 90%, preferably from 99.9 to 99%

Suspension Concentrates:

active ingredient mixture: from 5 to 75%, preferably from 10 to 50%

water from 94 to 24%, preferably from 88 to 30%

surface-active agent: from 1 to 40%, preferably from 2 to 30%

Wettable Powders:

active ingredient mixture: from 0.5 to 90%, preferably from 1 to 80%

surface-active agent: from 0.5 to 20%, preferably from 1 to 15%

solid carrier: from 5 to 95%, preferably from 15 to 90%

Granules:

active ingredient mixture: from 0.1 to 30%, preferably from 0.1 to 15%

solid carrier: from 99.5 to 70%, preferably from 97 to 85%

The Examples that follow illustrate the invention further. They do notlimit the invention.

FORMULATION EXAMPLES

F1. Emulsifiable concentrates a) b) c) d) active ingredient mixture 5%10% 25% 50% calcium dodecylbenzenesulfonate 6%  8%  6%  8% castor oilpolyglycol ether 4% —  4%  4% (36 mol of ethylene oxide) octylphenolpolyglycol ether —  4% —  2% (7-8 mol of ethylene oxide) cyclohexanone —— 10% 20% aromatic C₉-C₁₂hydrocarbon mixture 85%  78% 55% 16%

Emulsions of any desired concentration can be prepared from suchconcentrates by dilution with water. F2. Solutions a) b) c) d) activeingredient mixture  5% 10% 50% 90% 1-methoxy-3-(3-methoxy- — 20% 20% —propoxy)-propane polyethylene glycol (mol. wt. 400) 20% 10% — —N-methyl-2-pyrrolidone — — 30% 10% aromatic C₉-C₁₂hydrocarbon mixture75% 60% — —

The solutions are suitable for application in the form of micro-drops.F3. Wettable powders a) b) c) d) active ingredient mixture 5% 25%  50% 80% sodium lignosulfonate 4% — 3% — sodium lauryl sulfate 2% 3% —  4%sodium diisobutylnaphthalenesulfonate — 6% 5%  6% octylphenol polyglycolether — 1% 2% — (7-8 mol of ethylene oxide) highly dispersed silicicacid 1% 3% 5% 10% kaolin 88%  62%  35%  —

The active ingredient is mixed thoroughly with the adjuvants and themixture is thoroughly ground in a suitable mill, affording wettablepowders which can be diluted with water to give suspensions of anydesired concentration. F4. Coated granules a) b) c) active ingredientmixture 0.1% 5% 15% highly dispersed silicic acid 0.9% 2%  2% inorganiccarrier material 99.0% 93%  83% (diameter 0.1-1 mm) for example CaCO₃ orSiO₂

The active ingredient is dissolved in methylene chloride, the solutionis sprayed onto the carrier, and the solvent is subsequently evaporatedoff in vacuo. F5. Coated granules a) b) c) active ingredient mixture0.1% 5% 15% polyethylene glycol (mol. wt. 200) 1.0% 2%  3% highlydispersed silicic acid 0.9% 1%  2% inorganic carrier material 98.0% 92% 80% (diameter 0.1-1 mm) for example CaCO₃ or SiO₂

The finely ground active ingredient is uniformly applied, in a mixer, tothe carrier material moistened with polyethylene glycol, yieldingnon-dusty coated granules. F6. Extruder granules a) b) c) d) activeingredient mixture 0.1% 3% 5% 15% sodium lignosulfonate 1.5% 2% 3%  4%carboxymethylcellulose 1.4% 2% 2%  2% kaolin 97.0% 93%  90%  79%

The active ingredient is mixed with the adjuvants, and the mixture isground, moistened with water, extruded and then dried in a stream ofair. F7. Dusts a) b) c) active ingredient mixture  0.1%  1%  5% talcum39.9% 49% 35% kaolin 60.0% 50% 60%

Ready-to-use dusts are obtained by mixing the active ingredient with thecarriers and grinding the mixture in a suitable mill. F8. Suspensionconcentrates a) b) c) d) active ingredient mixture   3%  10%  25%  50%ethylene glycol   5%   5%   5%   5% nonylphenol polyglycol ether —   1%  2% — (15 mol of ethylene oxide) sodium lignosulfonate   3%   3%   4%  5% carboxymethylcellulose   1%   1%   1%   1% 37% aqueous formaldehydesolution 0.2% 0.2% 0.2% 0.2% silicone oil emulsion 0.8% 0.8% 0.8% 0.8%water  87%  79%  62%  38%

The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired concentration can be obtained by dilution with water.

It is often more practical to formulate MCPA, bromoxynil, the compoundof formula I and the mixing partner of formula II separately and then,shortly before application, to bring them together in the applicator inthe desired mixing ratio in the form of a “tank mixture” in water. Theability of the safeners of formula II to protect cultivated plantsagainst the phytotoxic action of mixtures of MCPA, bromoxynil and thecompound of formula I is illustrated in the following Examples.

BIOLOGICAL EXAMPLE

Examples B1: Post-emergence applications of mixtures of MCPA, bromoxyniland the herbicide of formula I wherein R₁ and R₃ are —C₂H₅; R₄ and R₅together form a group —CR₁₄(R₁₅)—CR₁₆(R₁₇)—O—CR₁₈(R₁₉)—CR₂₀(R₂₁)—wherein R₁₄, R₁₅ R₁₆, R₁₇, R₁₈, R₁₉, R₂₀ and R₂₁ are hydrogen; and G iseither hydrogen (=herbicide H1) or (CH₃)₃CC(O)— (=herbicide H2), withthe safener of formula II wherein Rs₁ is chlorine and Rs₂ is1-methylhexyl, in wheat and barley, and together with 3 different weeds.

The test plants are grown to a post-application stage in pots undergreenhouse conditions. A standard soil is used as cultivation substrate.At a post-emergence stage, the herbicides, both on their own and inadmixture with the safener, are applied to the test plants or tocultivated plants seed-dressed with safener. The application is carriedout using an emulsion (prepared from a 25% emulsifiable concentrate(Example F1, b)) of the test substances using 500 litres of water perha. The rates of application depend on the optimum concentrationsascertained under field conditions and greenhouse conditions. The testsare evaluated after 9, 10, 20 and 24 days (100% action=plant iscompletely dead, 0% action=no phytotoxic action). The results obtainedshow that the safener used can significantly reduce the damage caused tothe cultivated plants by the herbicide mixture.

The same results are obtained when the active ingredient mixture isformulated in accordance with the other above-mentioned FormulationExamples.

1. A selectively herbicidal composition which, in addition to comprisingcustomary inert formulation adjuvants such as carriers, solvents andwetting agents, comprises as active ingredient a mixture of a) aherbicidally effective amount of a mixture of MCPA, bromoxynil and aherbicide of formula I

wherein R₁ and R₃ are each independently of the other ethyl, haloethyl,ethynyl, C₁- or C₂-alkoxy, C₁- or C₂-haloalkoxy, C₁- or C₂-alkylcarbonylor C₁- or C₂-hydroxyalkyl; R₄ and R₅ together are a groupZ₂-CR₁₄(R₁₅)—CR₁₆(R₁₇)—O—CR₁₈(R₁₉)—CR₂₀(R₂₁)-(Z₂); R₁₄, R₁₅, R₁₆, R₁₇,R₁₈, R₁₉, R₂₀ and R₂₁, are each independently of the others hydrogen,halogen, C₁-C₄alkyl or C₁-C₄haloalkyl, it being possible for an alkylenering to be either fused or spiro-linked to the carbon atoms of the groupZ₂, which alkylene ring contains, together with the carbon atoms of thegroup Z₂ to which it is bonded, from 2 to 6 carbon atoms and may beinterrupted by oxygen, or that alkylene ring bridges at least one ringatom of the group Z₂; G is hydrogen, —C(X₁)—R₃₀, —C(X₂)—X₃—R₃₁,—C(X₄)—NR₃₂(R₃₃), —S(O)₂—R₃₄, —P(X₅)R₃₅R₃₆, —CH₂—X₆—R₃₇ or an alkalimetal cation, alkaline earth metal cation, sulfonium cation or ammoniumcation; X₁, X₂, X₃, X₄, X₅ and X₆ are each independently of the othersoxygen or sulfur; R₃₀, R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆ and R₃₇ are eachindependently of the others hydrogen, C₁-C₁₀alkyl, C₁-C₁₀haloalkyl,C₁-C₁₀cyanoalkyl, C₁-C₁₀nitroalkyl, C₁-C₁₀aminoalkyl, C₂-C₅-alkenyl,C₂-C₅haloalkenyl, C₃-C₈cycloalkyl, C₁-C₅alkylamino-C₁-C₅alkyl,di(C₁-C₅alkyl)amino-C₁-C₅alkyl, C₃-C₇cycloalkyl-C₁-C₅alkyl,C₁-C₅alkoxy-C₁-C₅alkyl, C₃-C₅alkenyloxy-C₁-C₅alkyl,C₃-C₅alkynyloxy-C₁-C₅alkyl, C₁-C₅alkylthio-C₁-C₆alkyl,C₁-C₅alkylsulfoxyl-C₁-C₅alkyl, C₁-C₅-alkylsulfonyl-C₁-C₅alkyl,C₂-C₈alkylideneaminooxy-C₁-C₅alkyl, C₁-C₅alkylcarbonyl-C₁-C₅alkyl,C₁-C₅alkoxycarbonyl-C₁-C₅alkyl, C₁-C₅alkylaminocarbonyl-C₁-C₅alkyl,di(C₁-C₆alkyl)amino-carbonyl-C₁-C₅alkyl,C₁-C₅alkylcarbonylamino-C₁-C₅alkyl,C₁-C₅alkylcarbonyl(C₁-C₅alkyl)-amino-C₁-C₅alkyl, tri(C₁- orC₂-alkyl)silyl-C₁-C₅alkyl, phenyl, heteroaryl, phenyl-C₁-C₅alkyl,heteroaryl-C₁-C₅alkyl, phenoxy-C₁-C₅alkyl or heteroaryloxy-C₁-C₅alkyl,it being possible for the afore-mentioned aromatic rings to besubstituted by halogen, nitro, cyano, amino, di(C₁-C₄alkyl)amino,hydroxy, methoxy, ethoxy, methylthio, ethylthio, formyl, acetyl,propionyl, carboxyl, C₁-C₅alkoxycarbonyl or by C₁- or C₂-haloalkyl; R₃₄,R₃₅ and R₃₆ are, in addition, C₁-C₁₀alkoxy, C₁-C₁₀haloalkoxy,C₁-C₅alkylamino, di(C₁-C₅alkyl)amino, benzyloxy or phenoxy, it beingpossible for the aromatic rings of the last two substituents to besubstituted by halogen, nitro, cyano, amino, dimethylamino, hydroxy,methoxy, ethoxy, methylthio, ethylthio, formyl, acetyl, propionyl,carboxyl, C₁-C₅alkoxy-carbonyl or by C₁- or C₂-haloalkyl; and R₃₇ is, inaddition, C₁-C₁₀alkylcarbonyl, or a salt or diastereoisomer of acompound of formula I, and b) an amount, effective for herbicideantagonism, of a safener of formula II

wherein Rs₁ is hydrogen or chlorine and Rs₂ is hydrogen, C₁-C₈alkyl, orC₁-C₈alkyl substituted by C₁-C₆alkoxy or by C₃-C₆alkenyloxy.
 2. Acomposition according to claim 1, which comprises, as compound offormula II, a compound of that formula wherein Rs₁ is chlorine and Rs₂is C₁-C₈alkyl.
 3. A composition according to claim 1, which comprises,as compound of formula I, a compound of that formula wherein R₁ and R₃are each independently of the other ethyl, haloethyl, ethynyl, C₁- orC₂-alkoxy or C₁- or C₂-haloalkoxy.
 4. A composition according to claim1, which comprises, as compound of formula I, a compound of that formulawherein R₄ and R₅ together form a groupZ₂-CR₁₄(R₁₅)—CR₁₆(R₁₇)—O—CR₁₈(R₁₉)—CR₂₀(R₂₁)-(Z₂) wherein R₁₄, R₁₅, R₁₆,R₁₇, R₁₈, R₁₉, R₂₀ and R₂₁, are hydrogen.
 5. A composition according toclaim 1, which comprises, as compound of formula I, a compound of thatformula wherein G is hydrogen, —C(X₁)—R₃₀, —C(X₂)—X₃-R₃₁,—C(X₄)—NR₃₂(R₃₃), —S(O)₂—R₃₄, —P(X₅)R₃₅R₃₆, —CH₂—X₆—R₃₇ or an alkalimetal cation, alkaline earth metal cation, sulfonium cation or ammoniumcation; X₁, X₂, X₃, X₄, X₅ and X₆ are each independently of the othersoxygen or sulfur; R₃₀, R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆ and R₃₇ are eachindependently of the others hydrogen, C₁-C₈alkyl, C₁-C₈haloalkyl,C₁-C₈cyanoalkyl, C₁-C₈nitroalkyl, C₁-C₈amino-alkyl, C₂-C₅alkenyl,C₂-C₅haloalkenyl, C₃-C₈cycloalkyl, C₁-C₅alkylamino-C₁-C₂alkyl,di(C₁-C₅alkyl)amino-C₁-C₂alkyl, C₃-C₇cycloalkyl-C₁-C₂alkyl,C₁-C₄alkoxy-C₁-C₄alkyl, C₂-C₄alkenyloxy-C₁-C₄alkyl,C₃-C₄alkynyloxy-C₁-C₄alkyl, C₁-C₄alkylthio-C₁-C₄alkyl,C₁-C₂alkylsulfoxyl-C₁-C₂alkyl, C₁-C₂alkylsulfonyl-C₁-C₂alkyl,C₂-C₈alkylideneaminooxy-C₁-C₂alkyl, C₁-C₅alkylcarbonyl-C₁-C₂alkyl,C₁-C₅alkoxycarbonyl-C₁-C₂alkyl, C₁-C₅alkylamino-carbonyl-C₁-C₂alkyl,di(C₁-C₄alkyl)aminocarbonyl-C₁-C₂alkyl,C₁-C₅alkylcarbonylamino-C₁-C₂alkyl,C₁-C₂alkylcarbonyl(C₁-C₃alkyl)amino-C₁-C₂alkyl, tri(C₁- orC₂-alkyl)silyl-C₁-C₃alkyl, phenyl, heteroaryl, phenyl-C₁-C₂alkyl,heteroaryl-C₁-C₂alkyl, phenoxy-C₁-C₂alkyl or heteroaryloxy-C₁-C₂alkyl;R₃₄, R₃₅ and R₃₆ are, in addition, C₁-C₆alkoxy, C₁-C₆haloalkoxy,C₁-C₃alkylamino, di(C₁-C₃alkyl)amino, benzyloxy or phenoxy, it beingpossible for the aromatic rings of the last two substituents to besubstituted by halogen, nitro, cyano, amino, dimethylamino, hydroxy,methoxy, ethoxy, methylthio, ethylthio, formyl, acetyl, propionyl,carboxyl, C₁-C₆alkoxycarbonyl or by C₁- or C₂-haloalkyl; and R₃₇ is, inaddition, C₁-C₈alkyl-carbonyl.
 6. A composition according to claim 5,which comprises, as compound of formula I, a compound of that formulawherein G is hydrogen, —C(X₁)—R₃₀, —C(X₂)—X₃—R₃i, —C(X₄)—NR₃₂(R₃₃),—S(O)₂-R₃₄, —P(X₅)R₃₅R₃₆, —CH₂—X6—R₃₇ or an alkali metal cation,alkaline earth metal cation, sulfonium cation or ammonium cation; X₁,X₂, X₃, X₄, X₅ and X₆ are each independently of the others oxygen orsulfur; R_(30, R) ₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆ and R₃₇, are eachindependently of the others hydrogen, C₁-C₈alkyl, C₁-C₈haloalkyl,C₂-C₅alkenyl, C₂-C₅haloalkenyl, C₃-C₈cycloalkyl,C₃-C₇cycloalkyl-C₁-C₂alkyl, C₁-C₄alkoxy-C₁-C₄alkyl, phenyl, heteroaryl,phenyl-C₁-C₂alkyl, heteroaryl-C₁-C₂alkyl, phenoxy-C₁-C₂alkyl orheteroaryloxy-C₁-C₂alkyl; R₃₄, R₃₅ and R₃₆ are, in addition,C₁-C₆alkoxy, C₁-C₃alkylamino, di(C₁-C₃alkyl)amino; and R₃₇ is, inaddition, C₁-C₈-alkylcarbonyl.
 7. A composition according to claim 1,which comprises a) a mixture of MCPA, bromoxynil and a herbicide offormula I wherein G is hydrogen or —C(X₂)—X₃—R₃₁, wherein X₂ and X₃ areoxygen, and R₃₁ is tert-butyl, and b) a safener of formula II whereinRs₁ is chlorine and Rs₂ is 1 -methylhexyl.
 8. A composition according toclaim 1, which comprises an additive comprising an oil of vegetableorigin, or an alkylated derivative thereof, or a mineral oil, or amixture thereof.
 9. A composition according to claim 8, which comprisesan additive comprising an oil of vegetable origin having the components(A) from 20 to 90% by weight of alkyl esters of higher (C₄-C₂₂) fattyacids, (B) from 4 to 40% by weight of anionic or non-ionic surfactants,(C) from 2 to 20% by weight of higher (C₁₀-C₂₀) fatty acids, and (D) upto 140% by weight, based on the total amount of components (A) to (C),of hydrocarbons.
 10. A composition according to claim 8, which comprisesan additive comprising an oil of vegetable origin having the components(A) C₁-C₄alkyl esters of C,₂-C,₈ fatty acids, (B) anionic surfactants ofthe dodecylbenzylsulfonate type, (C) C₁₂-C₁₈ fatty acids, and (D)aromatic hydrocarbons.
 11. A method of selectively controlling weeds andgrasses in crops of useful plants, which method comprises treating theuseful plants, their seeds or cuttings or the crop area thereof,simultaneously or separately, with a) a herbicidally effective amount ofa mixture of MCPA, bromoxynil and a herbicide of formula I, b) anamount, effective for herbicide antagonism, of a safener of formula IIand, optionally, c) an additive comprising an oil of vegetable origin,or an alkylated derivative thereof, or a mineral oil, or a mixturethereof.
 12. A method according to claim 11, which comprises treatingcrops of useful plants or areas for crops of useful plants with from0.005 to 0.5 kg/ha of the herbicidal mixture and an amount of from 0.001to 0.5 kg/ha of a safener of formula II.
 13. A method according to claim11, wherein the crop of useful plants is a cereal, maize or sorghum.